Preparation of polyvinylbenzene sulfonyl chlorides and derivatives thereof



inafter.

United States Patent PREPARATION OF POLYVINYLBENZENE SUL- FONYLCHLORIDES AND DERIVATIVES THEREOF Delbert D. Reynolds and John A.Cathcart, Rochester,

N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., acorporation of New Jersey No Drawing. Application December 9, 1952,Serial No. 325,026

Claims. c1. zen-79.3

This invention relates to the preparation of polyvinylbenzenesulfonylchlorides, and more particularlyto the preparation of thesulfonylchlorides of water-soluble sulfonated polystyrenes andderivatives thereof.

In pending application Serial No. 24,676, filed May 1, 1948, in thenames of Joseph B. Dickey and Theodore E. Stanin, now U. S. Patent No.2,618,655, and U. S. Pa'tent 2,616,917, dated November 4, 1952, of HarryW. Coover, Jr., and Joseph B. Dickey, describe the preparation ofcertain sulfonarnidostyrenes and polymers, and certain alkyl styrenesulfonates and polymers, respectively. On each of the above inventions,a monomeric haloarylalkane, e. g. l-bromo-I-phenyl ethane, 2-bromo-1phenyl ethane, etc., is sulfonated, reacted with a suitable alcohol oramine, dehydrohalogenated and then polymerized. While the above processdoes provide a method for preparing a number of resinous polystyrenesulfonamides and sulfonates, it is quite involved because of the severalconversions of monomers, dehydrohalogenation, loss of yield in eachstep, etc., and is also limited in its application, particularly wherecertain water-soluble sulfonaniides and sulfdnates having importance asgelatin addenda. or as other useful agents in photographic processes aredesired, the process failing to give. polymers having the requiredproperties. We have now found that highly satisfactory water-solublepolystyrene sulfonamides, and other polystyrene derivatives, can beprepared readily, and efficiently by converting a sulfonat'edpolystyrene to thecbrresponding acid chloride and then reacting the acidchloride with compounds containing a reactive hydrogen e. g. ammonia,ana'r'nine, an alcohol, an aminoalco'hol, et'c.

It is, accordingly, an object, of the invention to provide certainpolystyrene sulfonamides and sulfonat'es. Another object is to provide aprocess for their preparation. Still another object is to provide theintermediate acid chlorides of certain s'ulfonated polystyrenes andprocess for pireparing th'e same. Other objects will become apparenthere- In accordance with the inv nnmtwe prepare our resinous polystyrenesulfo'n'arhides and siilfonates by first sulfonating polystyrene inethylene chloride or other chlorinated aliphatic solvent, in thepresence of a co-ordination complex of sulfur tribxide and 8;8"-dichloroethyl ether. By varying the proportions of the reactants,products can be prepared having an average of about from 0.5 to 2sulfonic acid groupsper styrene unit, preferably from 0.75 to 1.25sulfonic acid groups per styrene unit. For further details of thesulfonation pro,t :edure',v reference can be had to M. Baer, U; S.Patents 2,533,210 and 2,533,211, each dated December- 12, 1-950. Afterisolation of the granular sulfonic acid derivative, it is suspended indry benzene or other inert reaction medium with powdered phosphoruspenta chloride and heated at from 35 to 80 C., until the conversion ofthe sulfonic acidgroups of sulfonyl chloride groupsis substantiallycomplete. The acid chloride ofthe sulfonated. polystyrene thus formed isfreed of phosphorus compoundsiby washing with water and by precipitationinto water from 2,725,368 Patented Nov. 29, 1955 .v ice a methyl ethylketone-acetone solution or dope, and can then be reacted with ammonia togive thecorresponding simple sulfonamides; with water to give thecorresponding sulfonic acids; with alcohols containing from 1 to 6carbon atoms (e. g. methanol, propanol, butanol, hexanol,N,N-dimethylaminoethanol N,N-dimethylaminopropanol, etc.) to give thecorresponding sulfonates; with primary and secondary aliphatic aminescontaining from 1 to 4 carbon atoms (e. g. methylamine, ethylamine,propylamine, isopropylamine, butylamine, dimethylamine, etc.) to givethe corresponding N-sub'stituted sulfonam'ides; with primary andsecondary aininoalcohols containing from 2 to 6 carbon atoms (e. g.ethanolamine, diethanolamine, 2 amino-l-butanol, hexanolamine; etc.) togive the corresponding N-hydroxyalkyl sulfonamides; with N,N-dialkylalkane diamines containing from 2 to 4 carbon atoms (e. g. N,N-dimethylethanediamine, N,N-dimethyl propanediamine, etc.) to give thecorresponding N,N-dialkylaminoalkyl sulfonamides; with arylamines (e. g.aniline, naphthalene, N-methy'l aniline, etc.) to give the correspondingN-aryl substituted sulfonamides; with heterocyclic amines (e. g. theC-amino pyridines such as 2- amino pyridine, etc.) to give thecorresponding N-heterocyclic group substituted snlfonamides; and similarresinous products with other compounds containing a reactive hydrogenatom. Ordinarily, an excess of the compound containing the reactivehydrogen is used, preferably from about 2 to 10 grain-moles: to eachgram-mole of the resinous acid chloride. Those of our resinous productscontaining free hydroxyl' groups are' especially characterized by beingwater-soluble and having particular photographic uses. However all ofthe resinous products prepared as above described are useful forpreparing v'ari'o'us coating and impregnating compositions, in suitablesolvents with or without, fillers, dyes, pigments, etc.

The following exampleswill serve to illustrate further the preparationof our intermediate .polyvinylbenzenesulfonyl chlorides andcertainderivatives thereof.

Example 1 A complex 'of/3,B'-dichloroethyl ether and sulfur trioxide wasprepared by dissolving 7i5 g. (approx. 5 mol) of B,B'-dichloroethylether in 2000 g. of ethylene'chlo'ride, cooling the solution to 4 C. orless and adding to solution, 200 g. 2.5 1101 of liquid sulfur trioxide(Sulfan B) with constant stirring and at such time that the temperatureremained at about 4 C. The solution of the complex just formed wasfurther cooled to -20 C. and a solution of g. (0.96 mol) of polystyrene(Lustrex 15, {7;} in benzene=0.65) in 1900 g. of ethylene chloride wasadded rapidly with good stirring. The temperature was kept below 5 C.while the polystyrene was added. Then the coolant was removed and thestirring continued for 30 minutes while the temperature rose to 15 C.The productwas filtered on coarse sintered glass funnels andWashedtwic'e with dry ether. After leaching the hygroscopic sulfonicacid for two hours with dry ether, it was filtered, then suspended intwo liters of dry benzene. The sulfonated polystyrene containedapproximately 0.75O.80 sulfonic acid groups per styrene unit. To thevigorously stirred suspension, contained in a 5-liter three-necked flaskfitted with thermometer, drying tube and condenser, was added 800 g.(approx. 3.8 mol) of powdered phosphorus pentachlo'ride. The suspensionwas warmed gradually to- 50 C., with evolution of hydrogen chloridebeginning at 40-45 C. After 4560 minutes at this temperature, ayellowing appeared followed by an agglomeration which. stopped thestirring. The temperature was held at 50 C. for 45 minutes longer ashydrogen chloride continued toevolve. After cooling somewhat, thebenzene wasdecanted andthestillwarm polymeric mass was poured ontocracked ice, stirred and broken up. The product was leached overnight inrunning tap water, then air-dried. A solution of the dried polymer inmethyl ethyl ketone-acetone (3:1) was filtered and precipitated intowater. After again washing overnight in running tap water, the acidchloride of the sulfonated polystyrene was dried before using. Analysisof the resinous product gave by weight an average value of 49.5 percentof carbon, 4.1 percent of hydrogen, 13.6 percent of sulfur and 13.6percent of chlorine compared with calculated theory (assuming one SO2C1group per styrene unit) of 47.4, 3.5, 15.8 and 17.5 percent for carbon,hydrogen, sulfur and chlorine, respectively. This indicates that thepolystyrene sulfonyl chloride obtained as above described hadapproximately 0.76 nuclear sulfonyl chloride (SOzCl) groups per styreneunit, i. e. a polymer comprising a minor portion by molar percentage ofunits and a major portion of OH2-CH-- units.

By varying the ratio of the polystyrene to the sulfonating agent in theabove example, final products can be prepared which contain from about0.5 to 2.0 sulfonyl chloride groups per styrene unit. The resinous acidchloride prepared as above described are soluble in organic solventssuch as dimethyl formamide, acetone, methyl ethyl ketone, etc.

Example 2 To a rapidly stirred solution of g. (approx. 0.05 mol) of apolyvinylbenzenesulfonyl chloride, obtained by the general process ofExample 1, in 100 cc. of acetone, there was slowly added a solution of10 cc. (approx. 0.15 mol NHa) of ammonium hydroxide diluted to 25 cc.with acetone. Stirring was continued for 14 hours, after which theproduct was precipitated into water, washed with alcohol-ether mixtureand dried. It was insoluble in water, but readily dissolved in alkalies.Analysis of the resinous product gave by weight 51.4 percent carbon, 5.5percent hydrogen, 11.4 percent sulfur, 6.1 percent nitrogen and less.than 1 percent of chlorine compared with calculated theory forpolyvinylbenzenesulfonamide comprising the recurring structural unit of52.5, 4.9, 17.5, and 7.65 per cent for carbon, hydrogen, sulfur andnitrogen, respectively.

Example 3 In the same manner as in above Example 2, 10 g. of thepolyvinylbenzenesulfonyl chloride were reacted with 15 g. of aniline.The product was precipitated into ether and dried. It was insoluble inwater, but readily dissolved in alkalies. Analysis of the resinousproduct gave by weight 63.5 percent of carbon, 5.6 percent of hydrogen,11.6 percent of sulfur, 4.7 percent of nitrogen, and less than 1 percentof chlorine compared with calculated theory forpolyvinylbenzenesulfonanilide comprising the recurring structural unitof 65.0, 5.0, 12.4 and 5.4 percent of carbon, hydrogen, sulfur andnitrogen respectively.

Example 4 To a Well-stirred solution of 10 g. of apolyvinylbenzenesulfonyl chloride, prepared as set forth in Example 1,in cc. of methyl ethyl ketone, there was slowly added 14 g. ofZ-aminopyridine in 50 cc. of methyl ethyl ketone. Stirring was continuedfor 4 hours, then the reaction mixture was allowed to stand for 18hours. The product was filtered, extracted with water and then dried. Itwas insoluble in water and in dilute acids, but readily dissolved inalcoholic potassium hydroxide. Analysis of the resinous product gave byweight 57.4 percent of carbon, 5.0 percent of hydrogen, 11.9 percent ofsulfur, 9.2 percent of nitrogen and less than 1 percent of chlorinecompared with calculated theory forpolyvinylbenzenesulfon-Z-amidopyridine comprising the recurring strucof60.0, 4.6, 12.3 and 12.3 and 10.2 percent of carbon, hydrogen, sulfurand nitrogen, respectively.

Example 5 To a well-stirred solution of 10 g. of apolyvinylbenzenesulfonyl chloride, prepared as set forth in Example 1,in cc. of dimethyl formamide and methyl ethyl ketone, there was slowlyadded a solution of 13 g. of p-arninoacetophenone in 30 cc. of methylethyl ketone. Stirring was continued for 3 hours as the mixture cleared.After standing for 65 hours, the product was precipitated into absoluteethanol. It was only swollen by water, but was soluble in alcohol-watermixtures and in dilute aqueous alkalies. The resinous product appearedto contain the recurring structural unit Example 6 To a suspension of 1part of polyvinylbenzenesulfonyl chloride in 10 parts of water, therewas added a drop of pyridine. With stirring, clearing began at once anda clear, colorless solution of polyvinylbenzene sulfonic acid wasobtained Within a few minutes.

Example 7 To a stirred solution of 10 g. of polyvinylbenzenesulfonylchloride, prepared as set forth in Example 1, in 75 cc. of dimethylformamide, there was slowly added 30 cc. of methanol containing 3 g. ofdissolved potassium hydroxide pellets. The reaction mixture was chilledin ice water and stirred for 4 hours. After storage for 65 hours, theproduct was precipitated into methanol, leached in methanol and dried.It was water-soluble. Analysis of the resinous product gave by weight50.0 percent of carbon, 4.7 percent of hydrogen, 12.5 percent of sulfurand less than 1 percent of chlorine compared with calculated theory forpolyvinyl methylbenzene sulfonate comprising the recurring structuralunit of 54.5, 5.05 and 16.2 percent of carbon, hydrogen and sulfur,respectively.

Example 8 To a stirred solution of 10 g. of polyvinylbenzenesulfonylchloride, prepared as set forth in Example 1, in 150 cc. of methyl ethylketone was added a solution of 6 g. of dimethylaminoethanol in 50 cc. ofmethyl ethyl ketone. Solid appeared quickly but stirring was continuedfor 4 hours, then the mixture was allowed to stand 18 hours. The productwas filtered out, washed with acetone, dissolved in ethanol-water andprecipitated into acetone. It was water-soluble and capable ofquaternization with tertiary nitrogen compounds. Analysis of theresinous product gave by weight 53.8 percent of carbon, 7.2 percent byweight of hydrogen, 11.0 percent of sulfur,

5.2 percent of nitrogen and less than 1.6 percent by weight of chlorinecompared with calculated theory for polyvinyl-2-dimethylaminoethylbenzene sulfonate comprising the recurring structural unit /CH3-CH7-CHC6H4SO2OCHz-OHz-N of 56.5, 6.6, 12.5 and 5.5 percent of carbon,hydrogen, sulfur and nitrogen, respectively.

Example 9 To a stirred solution of 10 g. of polyvinylbenzenesulfonylchloride, prepared as set forth in Example 1, in 75 cc. ofdimethylformamide, there was slowly added, with cooling, 12 g. ofethanolamine diluted with an equal volume of dime thylformamide.Stirring with cooling was continued for 30 minutes, then without coolingfor 30 minutes longer. After standing for about 3 hours, the product wasprecipitated into absolute ethanol, leached with ethanol and dried. Itwas Water-soluble. Analysis of the resinous product gave by weight 50.8percent of carbon, 5.8 percent of hydrogen, 12.9 percent of sulfur, 5 .2percent of nitrogen and less than 1 percent of chlorine compared withcalculated theory for polyvinylbenzene sulfon-(N-hydr'oxyethYl)-amidecomprising the recurring structural unit of 53.0, 5.7, and percent ofcarbon, hydrogen, sulfur and nitrogen; respectively.

Example 10 In the same manner as Example 9, 17 g. of Z-amino-lbutanolwas reacted with 10 g. of the polyvinylbenzenesulfonyl chloride to givea water-soluble resinous product which analyzed by weight 53.6 percentof carbon, 6.7 percent of hydrogen, 11.1 percent of sulfur, 4.3 percentof nitrogen and less than 1 percent of chlorine compared with calculatedtheory for polyvinylbenzenesulfon-(N-1- ethyl-2-hydroxyethyl)-amidecomprising the recurring structural unit of 56.5, 6.6, 12.5 and 5.5percent of carbon, hydrogen, sulfur and nitrogen, respectively.

Example 11 The process was the same as Example 9 except that 23 g. of2-amino-2-methylpentanol-4 was reacted with 10 g. of the sulfonylchlorideto give a water-soluble resinous product which analyzed byweight 56.0 percent of carbon, 7.4 percent of hydrogen, 7.3 percent ofsulfur, 4.0 percent of nitrogen and less than 1 percent of chlorinecompared with calculated theory forpolyvinylbenzenesulfon-(N-1-dimethyl-3-hydroxybutane)- amide comprisingthe recurring structural unit of 59.4, 7.4, 11.3 and 4.95 percent ofcarbon, hydrogen, sulfur and nitrogen, respectively.

Example 12 The process was the same as Example 9 except that 20 g. ofdiethanolamine was reacted with the 10 g. of polyvinylbenzenesulfonylchloride to give a water-soluble resinous product which analyzed byweight 51.0 percent of carbon, 6.6 percent of hydrogen, 9.4 percent ofsulfur, 4.8 percent of nitrogen and 2.3 percent of chlorine comparedwith calculated theory for polyvinylbenzenesulfon- 6(N,N-dihydroxyethyl) -amide comprising the recurring structural unitCH:CHzOH of 53.1, 6.3, 11.8 and 5.2 percent of carbon, hydrogen, sulfurand nitrogen, respectively.

Example 13 The process was the same as Example 9 except that 15 g. ofN,N-dimethyl-l,3 diaminopropane was reacted with the 10 g. ofpolyvinylbenzenesulfonyl chloride to give a water-soluble resinousproduct which analyzed by weight 51.1 percent of carbon, 6.0 percent ofhydrogen, 11.5 percent of sulfur, 5.3 percent of nitrogen and 0.0percent of chlorine compared with calculated theory forpolyvinylbenzenesulfon-(N 3 dirnethylaminopropyl)- amide comprising therecurring structural unit 1 CH3 of 58.3, 7.5, 11.9 and 10.4 percent ofcarbon, hydrogen, sulfur and nitrogen, respectively.

Example 14 A solution of 1 cc. of concentrated ammonium hydroxide in 30cc. of water was added, with stirring, to a solutionof 10 g. ofpolyvinylbenzenesulfonyl chloride, prepared as set forth in Example 1,in 100 cc. of acetone and 40 cc. of methyl ethyl ketone'. To the smooth,cloudy dope which was present at the end of 2.5 hours of stirring, therewas added from 0.5 to 1.0 cc. of pyridine. After initial clearing, acloudiness again appeared which increased until the stirrer was stoppedby precipitation of the polymer (about 1 hour). The solvents weredecanted, the polymer dissolved in dimethyl formamide and precipitatedinto percent ethyl alcohol and dried. It was soluble in water. Analysisof the resinous product gave by weight 54.4 percent of carbon, 5.6percent of hydrogen, 12.6 percent of sulfur, 4.5 percent of nitrogen andless than 1 percent of chlorine compared with calculated theory forpolyvinylbenzenesulfonamide comprising the recurring structural unitOH2-CHCsH SO2NH2 of 52.5, 4.9, 17.5 and 7.65 percent of carbon,hydrogen, sulfur and nitrogen, respectively. However, some sulfonicgroups also appear to be present.

Example 15 The process was the same as Example 14 except that 2 cc. ofconcentrated ammonium hydroxide was used. This product was less solublein Water than that formed in Example 14. it swelled in cold water andwas soluble in hot water and in alcohol-water mixtures. Analysis of theresinous product gave by weight 54.4 percent of carbon, 5.6 percent ofhydrogen, 12.6 percent of sulfur, 4.5 percent of nitrogen and less than1 percent of chlorine. However, some sulfonic groups also appear to bepresent.

By proceeding as set forth in the above examples, other valuableresinous products can be prepared. For example, by reacting certainwater-soluble amines in the presence of substantial amounts of water, itis possible to produce a second type of resinous amide, i. e. onecontaining some sulfonic acid groups. This is illustrated with Examples14 and 15 where the products result from the reaction of ammonia andwater with the polyvinyl benzenesulfonyl chloride to give resinousproducts which are soluble in either cold or hot water, whereas theproduct of Example 2 prepared with practically a non-aqueous ammonia hasno sulfonic acid groups and is insoluble in water. i

T he process for preparing the polyvinylbenzene sulfone acids of theinvention is subject to a number of variables,

for example, the starting materialpolystyrenemay be used in differentviscosities. Lower or higher degrees of sulfonation may be attained bychoice of the dioxanesulfur trioxide complex or the fl,B'-dichloroethylethersulfur trioxide complex as well as the choice of ratio of sulfurtrioxide to the coordinating agent. Within limits tried, using an excessof phosphorus pentachloride, there was no relation of degree of sulfonylchloride formation to time. However, by variation of the amount ofphosphorus pentachloride, it is possible to decrease the degree of acidchloride formation.

What We claim is:

1. A two-phase process for preparing a resinous acid chloride comprisingreacting in dry'benzene a suspension of a sulfonated polystyrenecontaining from 0.5 to 2.0 sulfonic acid groups per styrene unit withphophorus pentachloride, at a temperature of from 35 to 80 (3., untilthe reaction is substantially complete, and separating the insolubleresinous acid chloride product from the reaction mixture.

2. A two-phase process for preparing a resinous acid chloride comprisingreacting in dry benzene a suspension of a sulfonated polystyrenecontaining from 0.5 to 2.0 sulfonic acid groups per styrene unit withphosphorus pentachloride, in the ratio of from 2 to 10 gram-moles of thephosphorus pentachloride to each gram-mole of the sulfonatedpolystyrene, at a temperature of from 35 to 80 C., until the reaction issubstantially complete, and separating the insoluble resinous acidchloride product from the reaction mixture.

3. A two-phase process for preparing a resinous acid chloride comprisingreacting in dry benzene a suspension of a sulfonated polystyrenecontaining approximately 0.750.80 sulfonic acid groups per styrene unitwith phosphorus pentachloride, in the ratio of from 2 to l gram-moles ofthe phosphorus pentachloride to each grammole of the sulfonated styrene,at a temperature of from to (3., until the reaction is substantiallycomplete, and separating the insoluble resinous acid chloride productfrom the reaction mixture.

4. A two-phase process for preparing a resinous acid chloride comprisingreacting in dry benzene a suspension of a sulfonated polystyrenecontaining approximately 0.5 suifonic acid groups to each styrene unitwith phosphorus pentachloride, in the ratio of from 2 to 10 gram-molesor the phosphorus pentachloride to each gram-mole of the sulfonatedpolystyrene, at a temperature of from 35 to 80 C., until the reaction issubstantially complete, and separating the insoluble resinous acidchloride product from the reaction mixture.

1 5. A two-phase process for preparing a resinous acid chloridecomprising reacting in dry benzene a suspension of a sulionatedpolystyrene containing approximately 2.0 sulfonic acid groups to eachstyrene unit With phosphorus pentachloride, in the ratio of from 2 to 10gram-moles of the phosphorus pentachloride to each gram-mole of thesulfonated polystyrene, at a temperature of from 35 to 80 C., until thereaction is substantially complete, and separating the insolubleresinous acid chloride product from the reaction mixture.

References Cited. in the file of this patent UNITED STATES PATENTS2,604,456 Signer July 22, 1952 2,615,000 Bradley Oct. 21, 1952 2,676,896Cohen Apr. 27, 1954 OTHER REFERENCES Whitmore: Organic Chemistry, pages167, 189, 772 and 773, Van Nostrand (1937).

1. A TWO-PHASE PROCESS FOR PREPARING A RESINOUS ACID CHLORIDE COMPRISINGREACTING IN DRY BENZENE A SUSPENSION OF A SULFONATED POLYSTYRENECONTAINING FROM 0.5 TO 2.0 SULFONIC ACID GROUPS PER STYRENE UNIT WITHPHOPHORUS PENTACHLORIDE, AT A TEMPERATURE OF FROM 35 TO 80* C., UNTILTHE REACTION IS SUBSTANTIALLY COMPLETE, AND SEPARATING THE INSOLUBLERESINOUS ACID CHLORIDE PRODUCT FROM THE REACTION MIXTURE.